Theoretical Study of the Oxidation of Methane to Methanol by the [(CuCuII)-Cu-II(mu-O)(2)Cu-III(7-N-Etppaz)](1+) Complex
文献类型：期刊论文
| 作者 | Liu, Yan Fang1; Du, Likai2
|
| 刊名 | INORGANIC CHEMISTRY
 |
| 出版日期 | 2018-03-19 |
| 卷号 | 57期号:6页码:3261-3271 |
| ISSN号 | 0020-1669 |
| DOI | 10.1021/acs.inorgchem.8b00054 |
| 文献子类 | Article |
| 英文摘要 | The reactivity patterns of a series of trivalent copper complexes have been studied to gain a better understanding of the chemical reactions occurring at the active site of particulate methane monooxygenase (pMMO). In this study, hybrid density functional theory is used to study the oxidation of methane to methanol mediated by the [(CuCuII)-Cu-II(mu-O)(2)Cu-III(7-N-Etppz)](1+) complex. Reaction mechanisms in different spin states were explored. Based on the calculated free-energy profile, a mechanism is suggested for the reaction of the oxidation of methane to methanol. The first step (1 -> 2) is a hydrogen transfer to the bridged oxygen in the Cu2O2 core from the methane to form a methyl radical. The second step (2 -> 3) is the radical recombination, in which the bridged hydroxyl rotates upward and exposes the oxygen moiety toward the methyl radical to form methanol. The radical recombination step is rate-limiting, with a calculated free-energy barrier of 19.6 kcal mol(-1), which is in good agreement with the experimental value of 18.4 kcal mol(-1). The mixed valent bis(mu-oxo)(CuCuIII)-Cu-II species in the Cu3O4 core is directly responsible for the C-H activation of methane. |
| WOS关键词 | DICOPPER SITE ; MONOOXYGENASE ; HYDROXYLATION ; DENSITY ; CONVERSION ; REACTIVITY ; SPECTROSCOPY ; ACTIVATION ; MECHANISM ; DFT |
| WOS研究方向 | Chemistry |
| 语种 | 英语 |
| WOS记录号 | WOS:000428219500038 |
| 出版者 | AMER CHEMICAL SOC |
| 资助机构 | National Science Foundation of China(21607164 ; 21503249) |
| 源URL | [http://ir.qibebt.ac.cn/handle/337004/10801]  |
| 专题 | 中国科学院青岛生物能源与过程研究所 |
| 通讯作者 | Liu, Yan Fang; Du, Likai |
| 作者单位 | 1.Chinese Acad Sci, Qingdao Inst Bioenergy & Bioproc Technol, Qingdao Key Lab Solar Energy Utilizat & Energy St, Key Lab Biobased Mat, Qingdao 266101, Shandong, Peoples R China 2.Huazhong Agr Univ, Coll Informat, Hubei Key Lab Agr Bioinformat, Wuhan 430070, Hubei, Peoples R China |
| 推荐引用方式 GB/T 7714 | Liu, Yan Fang,Du, Likai. Theoretical Study of the Oxidation of Methane to Methanol by the [(CuCuII)-Cu-II(mu-O)(2)Cu-III(7-N-Etppaz)](1+) Complex[J]. INORGANIC CHEMISTRY,2018,57(6):3261-3271. |
| APA | Liu, Yan Fang,&Du, Likai.(2018).Theoretical Study of the Oxidation of Methane to Methanol by the [(CuCuII)-Cu-II(mu-O)(2)Cu-III(7-N-Etppaz)](1+) Complex.INORGANIC CHEMISTRY,57(6),3261-3271. |
| MLA | Liu, Yan Fang,et al."Theoretical Study of the Oxidation of Methane to Methanol by the [(CuCuII)-Cu-II(mu-O)(2)Cu-III(7-N-Etppaz)](1+) Complex".INORGANIC CHEMISTRY 57.6(2018):3261-3271. |
入库方式： OAI收割
来源：青岛生物能源与过程研究所
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